Trinuclear dyes containing a 5-thiazolidone nucleus



i atented Oct. 20, 195$ TRINUCLEAR DYES CONTAINING A S-THIAZOLIDONENUCLEUS Per Aubert, Oslo, Norway, and Roy A. Jefireys and Edward B.Knott, Harrow, England, assignors to Eastman Kodak Company, Rochester,N. Y., a corporation of New Jersey No Drawing. Application March 2,1951, Serial No. 220,332

8 Claims. (01. 260--240.1) 1 2 This invention relates to trinuclear dyesconcarbon atoms in the cycloalkyl ring), e and n taining a5-thiazolidone nucleus and to methods each represents a positive integerfrom 1 to 2, for preparing them. More particularly, this in- (1represents a positive integer from 1 to 3, X vention relates totrinuclear dyes useful in alter- H represents an anion, such as Cl, Br",I-, C104", ing the sensitivity of photographic silver halidep-CH3-C6H4--SO3, C6E5-SO3", CHSCOC", emulsions. SCN-. etc., L representsa methine group, Z and Trinuclear dyes obtained from merocyanine Z1 eachrepresents the non-metallic atoms necesdyes containing a rhodaninenucleus have presary to complete a heterocyclic nucleus containviouslybeen described. Fry et al. U. S. Patent h ing from five to six atoms inthe heterocyclic 2,388,963, dated November 13, 1945. Such dyes, h) ring,such as those selected from the group conin certain cases, canadvantageously be employed sisting of those of the thiazole series (e.g. thiin altering the sensitivity of photographic silver azole, 4methylthiazole, 4 phenylthiazole, 5- halide emulsions. methylthiazole,5-phenylthiazo1e, 4,5 dimethyl- We have now found a new class oftrinuclear thiazole, 4,5-dipheny1thiazole, 4 (2 thienyD- dyes which canalso be used in altering the senthiazole, etc.), those of thebenzothiazole series sivity of photographic silver halide emulsions. (e.g. benzothiazole, 4-chlorobenzothiazo1e, 5-

It is, therefore, an object of our invention to chlorobenzothiazole,6-chlorobenzothiazole, '7- provide new trinuclear dyes. A further objectchlorobenzothiazole, 4-methylbenzothiazole, 5- is to provide methods forpreparing these dyes. methylbenzothiazole, 6-methy1benzothiazo1e, 5-Still another object is to provide photographic bromobenzothiazole, 6-bromobenzothiazo1e, 4- silver halide emulsions containing these newdyes, phenylbenzothiazole, 5 phenylbenzothiazole, 4 and methods forpreparing these emulsions. methoxybenzothiazole, 5-methoxybenzothiazole, Other objects will become apparent from a conmet0XybenZ0thiazo1e, fi-iodobenzothiazole, 6- sideration of the followingdescription and exodobenzothiazole, 4 ethoxyb nzothi 5 amp1esethoxybenzothiazole, tetrahydrobenzothiazole, 5,

According to our invention we provide tri- 6-dimeth0xybenzothiazole, 5,6-dioxymethylenenuclear dyes selected from those represented by nzotiazole, 5 hydroxybenzothiazole, 6 hy the following two general formuldroxybenzothiazole, etc.), those of the naphthothiazole series (e. g.a-naphthothiazole, p-naphwherein R, R1, and R2 each represents an alkyl4-methyloxazo1e, 5-methyloxazole, 4-pheny1oxgroup, such as methyl, et ysop y -propy azole, 4,5-diphenyloxazole, 4-ethyloxazo1e, 4,5-din-butyl,isobutyl, n-amyl, n-heptyl, n-octyl, {3- methyloxazole, 5-phenyloxazole,etc.), those of hydroxyethm, p-acetoxyethyl, etc. groups (e. g. thebenzoxazole series (e. g. benzoxazole, 5-chloan alkyl group of theformula CmH2m+1 wherein 4-5 robenzoxazole, 5-methylbenzoxazole,S-phenylm represents a positive integer from 1 to 8),benzoxazole,'G-methylbenzoxazole, 5,6-dimethy1- and R1 can, in addition,represent alkyl groups, benzoxazole, 4,6 dimethylbenzoxazole, 5 methh asthe cycloalkyl groups, e. g. cyclopropyl, oxybenzoxazole, fiethoxybenzoxazole, 5-ch1orocyclobutyly yclopentyl, cyclohexyl, etc.groups benzoxazole, 6-methoxybenzoxazole, S-hydroxy- (e. g. cycloalkylgroups containing from 3 to 6 5o benzoxazole, fi-hydroxybenzoxazole,etc.), those of the naphthoxazole series (e. g. a-naphthoxazole,p-naphthoxazole, etc), those of the selenazole series (e. g.4-methylselenazole, 4-phenylselenazole, etc.), those of thebenzoselenazole series (e. g. benzoselenazole, 5 chlorobenzoselenazole,5 methoxybenzoselenazole, 5 hydroxybenzoselenazole,tetrahydrobenzoselenazole, etc.) those of the naphthoselenazole series(e. g. anaphthoselenazole, fl-naphthoselenazole, etc).

those of the naphthoselenazole series (e. g. a-

dine series (e. g. pyridine, 5-methylpyridine, ctc.),

etc., and Q represents the non-metallic atoms necessary to complete aheterocyclic nucleus containing from five to six atoms in theheterocyclic ring, such as those selected from the group consisting of athiazolone nucleus, for example, a 2,4(3,5)-thiazoledione nucleus, suchas 2,4(3,5) thiazoledione, 3-ethyl-2,4(-3,5)-thiazoledione, 3-phenyl-2,4(3,5) -thiazoledione or 3-naphthyl-2,-4 (3,5)-thiazoledionenuclei, a -2-thio-2-,4(3,5) -thiazoledione (a rhodanine) nucleus, suchas 3-alkyl- 2-thio-2,4(3,5) -thiazoledione (3-alkylrhodanine) 3phenyl-2-thio-2,4(3,5) thiazoledione (3 phenylrhodanine), 3naphthyl-Z-thio-ZA(3.5) thiazoledione (3-naphthylrhodanine) nuclei or 3-(l-benzothiazyl) -2-thio 2,4(3.5)-thiazoledione (3-(1-benzothiazyl-)-rhodanine) nuclei, 9, 2-thio- 2,5(3,4) -thiazoledione nucleus, such as3-methyl- 2-thio-2,5(3,4 thiazoledione, 3-ethyl-2-thio-2,5 (3,4)-thiazo1edione, 3-n-heptyl-2,5 (3,4) -thia'zoledione,3-cyclohexyl-2,'5(3,4) -thiazoledione, etc., a2-alkylmercapto-4(5)-thiazolone nucleus, such as2-ethylmercapto-4(5)-thiazolone, a thiazolidone nucleus, such as4-thiazolidone or its 3-alkyl-3-phenyl or 3-naphthyl derivatives, 2.2-alkylphenylamino-4(5) -thiazolone nucleus, or a 2-diphenylamino-4(5)-thiazolone nucleus; an oxazolone nucleus, for example, a'2-thio-2,4(3,'5) oxazoledione nucleus, such as a 3-alkyl-2-thio-2A(3,5)-oxazoledione nucleus; an imidazolone nucleus, for example a2,4(3,5)-imidazoledione nucleus, such as 2,4(3,5) -imidazoledione(hydantoin) or its 3-alkyl, 3-phenyl or 3-naphthyl derivatives as wellas its 1,3-diallzyl, 1-alky1-3-phenyl, 1-alkyl-3-naphthyl, 1,3 diphenyl,etc., derivatives, a 2-thio-2,4(3,5)-imidazoledione nucleus, such as2-thio-2,4(3,5)-imidazoledione (Z-thiohydantoin) or its 3-alkyl,3-phenyl or 3-naphthyl derivatives as well as its 1,3-dialkyl,l-alkyl-B- phenyl, l-alkyl-B-naphthyl, 1,3-diphenyl, etc., derivatives,a 2-alkylmercapto-5(4) -imidazolone, such as2-propylmercapto-5(4)-imidazolone; a thionaphthenone nucleus, such as2-(1) thionaphthenone or 1(2) thionaphthenone, a pyrazolone nucleus, anoxindole nucleus, such as 2,3- dihydro-B-ketoindole, and likefive-membered heterocyclic nuclei, a 2,4,6-triketohexahydropyrimidinenucleus, for example barbituric acid or 2-thiobarbituric acid, as wellas their l-alkyl or 1,3-dialkyl derivatives; 9. 3,4-dihydro-2 l)-quinclone nucleus, such as 3,4-dihydro-2(1)-quinolone(dihydrocarbostyril) a 3,4 dihydro-2(1)- quinoxalone nucleus, such as3,4-dihydro-2(1)- quinoxalone (oxydihydroquinoxaline) 3-phenomorpholone(l,4,2-benzoxazine-3(4)-one or benzo-fl-morpholone) nuclei;1,4,2-benzothiazine-3 (4)-one (ketodihydrobenzoparathiazine) nuclei, andthe like six-membered heterocyclic nuclei. The dyes wherein Q representsthe non-metallic atoms necessary to complete a heterocyclic nucleuscontaining five atoms in the heterocyclic ring, three of said atomsbeing carbon atoms, one of said atoms being a nitrogen atom, and theother of said atoms being a sulfur atom, a nitrogen atom, or an oxygenatom, have been found to be especially well adapted to the manufactureof photographic emulsions, we have found.

The new trinuclear dyes represented by Formula I above canadvantageously be prepared by condensinga compound selected from thoserepresented by the following general formula:

wherein R, R1, L, n, d, and Z have the values set forth above, and R3represents an alkyl group, such as methyl, ethyl, n-hexyl, etc. groups,and X1 represents an anion, such as those represented by X above, forexample, with a compound selected from those represented by thefollowing general formula:

IV Q

wherein Q has the values set forth above.

The new trinuclear dyes represented by Formula II above canadvantageously be prepared by condensing a compound selected from thoserepresented by Formula HI above with a cyclammonium quaternary saltselected from those represented by the following general formula:

wherein R2, Z1, X, and e have the values set forth above.

The condensations can advantageously be carried out in the presence of abasic condensing agent, such as the trialkylamines, e. g. triethylamine,tri-n-propylamine, tri-n-butylamine etc., dialkylanilines, e. g.N,N-dimethylaniline, N,N- diethylaniline, etc., N-alkylpiperidines, e.g. N- methylpiperidine, N-ethylpiperidine, etc., heterocyclic amines. e.g. pyridine, quinoline, isoquinoline, etc., N-alkylpyrroles, e. g.N-methylpyrrole, etc.

The-condensations can also be carried out in the presence of an inertsolvent, such as the lower aliphatic alcohols, e. g. ethyl, n-propyl,isopropyl, n-butyl, isobutyl, etc. alcohols, diethyl ether,.1,4-dioxane,'benzene, n-hexane, etc. Heat accelcrates thecondensations, and temperatures varying from about 25 C. to the refluxtemperature of the reaction mixture can be used.

The intermediates represented by Formula III above can advantageously beprepared by heating ayesdesi a compound selected from those representedby the following general formula:

wherein R, R1, n, d, L, and Z have the values given above, with an alkylsalt, such as those represented by the following general formula:

VII Rs-Xi wherein R1 and X1 have the values set forth above.

The intermediates represented by Formula VI above can be prepared asdescribed in the copending application S. N. 203,526, filed on December29, 1950, of R. A. Jeffreys and E. B. Knott. Intermediates of the typerepresented by Formula VIII above have been previously described by Cooke at al., Jour. Chem. Soc. (1949), DD. 1435-7.

The following examples describe more fully the manner whereby we preparecertain of the intermediates represented by Formula III above.

Example 1.-[2 (s ethyZbenzoxazoleHM-(Z- methylthio (4) thiazolone)ldimethinemerocyanine metho-p-toluenesulfonate 0=0--s C=CH CH=l t 2H5CH: 0.32 g. of [2-(3-ethylbenzoxazole) [4 (3- methyl-2-thio-2,5(3,4)thiazoledione) ldimethinemerocyanine and 0.2 g. of methylp-toluenesulfonate were heated together for minutes at 140 C. Thereaction mixture set to a solid, and it was then ground to a powder andwashed with dry benzene. It was recrystallized from an ethanol-diethylether mixture as red prisms with a blue reflex having a melting point of222 C. It sensitized a gelatino silver chloride emulsion with a maximumat 510 ma and a gelatino silver bromide emulsion with a maximum at 530ma.

Example 2.---[2-(3-ethylbenzoxazole) [4-,(2-ethylthz'o 5 (4) thiazoloneHdimethinemerocyam'ne metho-p-toluenesuljonate 1.0 g. of[2-(3-ethylbenzoxazole)] [4-(2-ethylthio 5(4) -thiazolone)ldimethinemerocyanine and 1.8 g. of'methyl p-toluene-sulfonate wereheated together for one hour at 130 C. The resulting semi-solid wasrecrystallized from. an

ethanol-diethyl ether mixture as fiat red needles melting at 209 C.

Example 3.[2-(3-ethylbenzomazole) l [4-(2-eth ylthio 5(4) thiazoloneHdimethinemerocyanine ethiodide 2.0 g. of[2-(3-ethylbenzoxazole)][4-(2-ethylthio 5(4)-thiazolone)]dimethinemerocyanine and 10 cc. of ethyl iodide were fused together in asealed tube at C. for 24 hours. The tube was then openedand the excessethyl iodide driven off. The residue was recrystallized from ethanol assoft, rust-colored needles having a melting point of 136 C.

Example 4.-[2 (3 ethylb-enzoxazole) [4 (2- ethylthio 5(4) thiazolone)lolimethinemerocyanine methomethylsulfate 1.0 g. of[2-(3-ethylbenzoxazole)][4-(2-ethy1- thio-5 (4) -thiazolone)ldimethylmerocyanine and 0.7 cc. of methyl sulfate were fused at C. for

30 minutes. The crude product was then washed with diethyl ether.

Example 5.,[4-(1-ethylquinoline) [4 (Z-methylthzo 5(4) thiazolone)ldz'methinemerocya- Example 6.[2 (B-ethylbenzoxazoleH [4 (2-methyZthio-S (4) -thiazolone) dimethinemerocyaninen-hepto-pt0luensalfonate zHl 1.0 g. of [2-(3-ethylbenzoxazole)lheptyl-2-thio-2,5 (3,4) -thiazoledione) [4- (3-ndimethinemerocyanine and0.5 g. of methyl p-toluenel sulfonate were heated together at 120 C. for30 minutes. The red solid obtained was ground to a powder, heated underreflux with benzene, and the benzene removed by decantation.

i? EmmpZe; i i-E2 (3 ethyllei: 1 42% methyZthio-5 (4) -thzazolone)dimethinamz-em cyanine atho-p-toluenesuljonate.

4.1 g. of [2-(3-ethylbenzoxazole) l L4-(3-ethyl- 2-thio-2,5 (3,4)-thiazoledione) dimethinemerocyanine and 2.53 g. of methylp-toluenesulfonate were heated at 120 C..for 30 minutes; The solid wasground. to a powder, washed, with diethyl ether,, and. then.recrystallized from an isopnopyl alcohol-diethyll ether mixture as anorange. microerystalline, powder melting, at 210 C. It, sensitized agelatino silver chloride emulsion with a. maximum at 510. my. and agelatino. silver. bromiodide emulsion with a.. maximum at 536 1119-.

Example 8.[2-(3-ethylbenzothiazole)] [4-(2- methylthz'o-fi'e)-thiazoloneI dimethinemerm cyanine GZICZOIWBQKO-QHIYOZUETLCSEUMW 0.6 g. of[2-(3-ethylbenzothiazoleH [4-(3- cyclohexyl-2-thio-2,5(3,4)thiazoledione)l dimethi'nemeroeyanine and 0&3 g. of methylp-toluenesul'fonate were heated together at: 120 C; for 30- minutes. Thesolid resulting was ground to a powder and washed diethyf ether. it wasfound to be deliquescent.

Example 9-.-E2.- (.i-ethylbenaowazolel 1* 54-42 methyZthz'o-5 (.4)-thiazolone) l dimethinememcyani'ne cyclohearo-p-toluenesulionate.

N 2H IHu 0.5 g. of [2-(3-ethylbenzoxazole)l[4-(3-cyclohexyl-2-thi0-2,5(3,4) -thiazoledione) l dimethinemerocyenineand 0 .28- g. of methyl p-toluenesulfonate were heated together for 30minutes at 120 C: The" resulting solidi was ground to a powder, washedwith diethyl ether, and'dried'. It was found to be deliquescent.

Example 1 0 .?--[2:-(S ethglbenzothiaaole)1: Lei-(.2;methyLthio-fifl)--thiazolone%l; dimetmnmem cyaninemetho-p-toluenesulfanmte' 4.3 g. of EZ-(B-ethylbenzothiazolell [4-(3-methy1-2-thio-2,5(3,4) -thiazo1edione) dimethi-nemerocyanine and 2.9 g.of methyl p-toluene sulfonate wereheated together at 130 62.. for 30Brmmpte tie-E2-tz-ethylbenzothiazolei:l 4962- ethylthz'o-5(4)thiazolonetl dimethinemerocyam'ne methomethylsulfate Example.12.[2-(3-methylthiazoline)l [4-(2- ethyZthio-5C4)thiazolonelldimethinemerocyamne mefltomet'hyl'sulfate The tollowing.examples; illustrate the manner whereby certain of the intermediatesrepresented by Formula. above can he prepared. Example.13.[2'-fif-etkylbenzomazele)l 54-(2- anytime-5(4) fliz'dzolo'ne) 1dimethinevmerocyanine iiHi 9.0 g. of N-(dithiocarbethoxy) glycine, 40.cc; of acetic anhydride, and 12 cc. of ethyl orthorformate were heated:together on' a steam bath for 30 minutes. The unreacted liquids werethen distilledofi? and the. residual oil consisting of 2 ethylthio 4ethoxymethylene 5(4') thiazolone was refluxed for five minutes: with 1&5g. of Z-methylbenzoxazoleethiodide', 4'0 cc; of; ethane and 101 cc: oftrietluyl'amiineand; the 1zeaction mixture then chilled. The resultingdye atter recrystallization; from ethanol formed fiat steel-blue:needles melting, at 156 0.. Example 14.-E2"(3'- methylthiazoZz'n-e) 1-[*efi- (-2- ethylth'i'o 5(4)I- tkzazolone) I dimethinemerocyanine:

This dye was prepared in the same manner as m nut The Solid product wground to a the dye of Example l-3 by replacing theZ-methylowder,washed. diethyfi 61513811 911 benzoxazole ethiodidebyamolecularlyequivalent cryst l z ti n fr an e -di t e r amount of Z-methylthiazoiinemethiodide. The mixture, it was obtained asmaroomleaflets me fi desiredproduct was: obtained as. maroon. needles ing at 182-? C. (6.2". g.)Itsensitized: bofli: a. gelatino silver chlorobromideemulsion and agelatino silverbromide; emulsion with zit-maximum: at 570 my,

at 129 C1. from ethanol.

The followingv examples willserve to illustrate the manner whereby we:prepare: our new; tri nucleaedyes... V l V Example15.--[2-(3-ethylbenzozazole)l [4 (5- oxo-2-phenyl-4-ozcazolinylidene) 3methyl-5- (4) -thiazolidone) l dimethinemerocyanine 0.5 g. of thequaternary salt obtained in Example i above and 0.18 g. of2-phenyl-5(4)-oxazolone were heated under reflux for four hours in thepresence of 10 cc. of ethanol and 0.15 cc. of triethylamine. Thereaction mixture was chilled and the solid filtered off. The dye wasrecrystallized from a pyridine-diethyl ether mixture as small bluishneedles melting at 310 C. It sensitized a gelatino silver chlorideemulsion with maxima at 540 and 570 ml and a gelatino silver bromideemulsion with a maximum at 610 m Example 16.-{2- (3-ethylbenzoxazole){2-[-4- (2 [3 ethylbeneoxaeolinylidene] ethylidene) -3-methyl-5(4)-thiazolone]} methinecyam'ne 0.5 g. of the quaternary salt obtained inExample 1 above, 0.3 g. of 2-methylbenzoxazole ethiodide, 0.15 cc. oftriethylamine, and 10 cc. of ethanol were heated under reflux for 4hours. The reaction mixture was chilled and the precipitate filteredofi. The dye, as recrystallized from methanol, melted at 300 C. and wasobtained as rey prisms. It sensitized a gelatino silver chlorideemulsion with maxima at 540 and 590 m and a gelatino silver bromideemulsion with a maximum at 590 m Example 17.-{2-(3-eihylbenzothiaeole)}{2[4- (2- [3-ethylbenzomazolinylidenel ethylidene) -3- methyl 5(4)thiazolonel} methinecyani'ne iodide 0.3 g. of the quaternary saltobtained in Example 1 above, 0.2 g. of 2-methylbenzothiazole ethiodide,0.12 cc. of triethylamine, and 6 cc. of ethanol were refluxed togetherfor one hour, chilled, and the reaction mixture filtered. The dye wasrecrystallized from pyridine as green needles melting at 286 C. Itsensitized a gelatino silver chloride emulsion with maxima at 520 and600 m and a gelatino silver bromide emulsion with a maximum at 630 m r.

Example .18.-{2-(3-methylthiazoline)} {2-[4- (2 [3ethylbenzozrazolylidene]ethylidene) -3- 3H5 0.3 g. of the quaternarysalt obtained in Ex 10 ample 1 above, 0.15 g. of 2-methylthiazolinemethiodide, 0.12 cc. of triethylamine, and 6 cc. of ethanol wererefluxed for one hour, chilled, and then filtered. The desired dye wasrecrystallized from methanol as red-bronze prisms melting at 298 C. Itsensitized a gelatino silver chloride emulsion with maxima at 520 and570 m and a. gelatino silver bromide emulsion with a maximum at 590 ma.

Example 19.--[4- (l-ethylquinoline) {2- [4- (4- [l-ethyl 1,4dihydroquinolinylidene] ethylidene) 3-methyl 5 (4)thiazolonenmethinecyanine iodide I 0.51 g. of the quaternary saltobtained in Example 5 above, 0.3 g. of lepidine ethiodide, 0.2 cc. oftriethylamine, and 10 cc. of ethanol were refluxed together for one houron the steam bath.

The reaction mixture was then chilled, and the precipitate collected ona filter. After recrystallization from aniline, the dye was obtained asa dark olive-green powder having a melting point of 234 C.

Example 20.[2- (1 -ethylquinoline) ]{2- [4- (2- [3ethylbenzoxazolinylidenel ethylidene) -3-n-heptyl-5 (4) -thiazolonel}methinecryanine iodide Example 21.--[4-(1-ethylquinoline)] {2-[4-(2-[3-ethylbenzoxazolinylidenel ethylidene)-3-nhepiyl 5(4) thiazolonel}methinecyanine iodide 0.5 g. of the quaternary salt obtained in Example6 above, 0.26 g. of lepidine ethiodide, 0.2 cc. of triethylamine, and 5cc. of ethanol were heated on a steam bath for 6 hours and the reactionmixture then chilled. The preeipitate was filtered off, and thenrecrystallized from a methanol-diethyl ether mixture as small moss-greenneedles melting at 184 C. -It sensitized a gela- 1 1 tino silverhromiodide emulsion with maxima at 640 and 700 m 0.9 g. of thequaternary salt obtained in Example 8 above, 0.25 g. of3-ethylrhodanine, 0.2 cc. of triethylamine and 10 cc. of ethanol werere- Iluxed on a steam bath for one hour, and the mixture chilled. Theprecipitate was collected on a filter and recrystallized from abenzenepetroleum ether mixture as grass-green needles melting at 239 C.It sensitized a gelatino silver chloride emulsion with maxima at 470 and.650 m and a gelatino silver bromiodide emulsion with a flat maximumlying between 52.0 and 680 mu.

Example 2.3. [2-(3a6thZ/Zb3722011l20l3) 1 {4-{2- (5-omo-2-n-octg thzo 4thiazolz'nylidene)-.3- .cyclohemyl-5-thz'azolidone]}dimethz'nemerocycame 01115 aHn ethylamine, and cc. of-ethanol, and theresulting solution was heated on a steam bath for 30 minutes and thenchilled. The precipitate was collected on a filter and recrystallizedfrom ligroin as yellow-green prisms melting at 150 C. It sensitized agelatino silver chloride emulsion" with maxima at 400 and 590 m and agelatino silver bromiodide emulsion with a maximum at 610 mu.

Example 24.[.2 .(3 a methylbenzothiazolefl {2- [4 (.2 l3ethylbeneomaaolinylidene] ethyl idene) -.3-.ethyl 5 .thz'azolidoneil}azamethinecyamne p-toluenesulfonate maxima at 400 and 560 m and agelat-ino silver bromiodide emulsion with a maximum 9.17 530 me- 12Example 2 5. ---{2-( 3-ethylbenaothiazole) M442- (3 methyl 5 --o.ro 2thio 4- thiazolidin ylidene) 3 methyl 5 thiazolindonefldi 1.04 .g. ofthe quaternary salt obtained in Example :10 above, 029 g. .of3-methyl-2-thio-15-thiazolidone .(Cook etal, Jour. Chem. Soc. (1949'),

page 2340) 0.2 .cc. of triethylamine, and "10 cc. of

ethanol were heated on a steam bath for minrates. and then chilled. Theprecipitate was collected ona filter (0.8 g.) and recrystallized from achloroform-petroleum ether mixture as a darkgreen microcrystallinepowder melting at 274 C.

It sensitized both gelatino-silver chlorobromide and silver bromideemulsions with a maximum at 580 m Example 26. {2-(3-ethylbeneothiazole)}{4- [2- (3 ethyl 4 01:0 2 tha'o 5 thiazolidinylidene) 3 methyl 5 thiazolidone]}dimethznemerocyanine 1.051: g. of thequaternary salt obtained in Example 10 above, 0.32 g. of'3-ethy'lrhodanine, 0.2 cc. of triethylamine, and 10 cc. of ethanol wereheated on a steam bath for- 20 minutes and then chilled. The precipitatewas collected on a filter (1.0 g.) and recrystallized from pyridine aslong indigo needles, melting at 300 C. It sensitized a gelatino silverchloro'bromide emulsion with a maximum at 670 m Example 27. {2-(3-ethylbenzothiazole)}{4-[2- (5 ozco 2 n octory 4 thiazolinylidene) "3-,methyl 5 .thzazolz'doncl}dimethinemero 5n cyanine 0.54 g. ofN-(thiocarbo-n-octoxy) glycine and $0 .5 cc. of acetic anthydride wereheated together on a steam bath for minutes. The unreacted aceticanhydride and acetic acid formed during the eraction were removed under.a vacuum. To the residual oil consisting of 2-n-octoxy-5(4)- thiazolonewere added 1.04 g. of the quaternary salt .obtainedin Example 10 .above0.3 c. of triethylamine and 10 cc. of ethanol, and. the mixture heatedon a steam bath for 20 minutes and then chilled. The dye which separatedweighed 0.9 g. and was recrystallized from a benzenepetroleum ethermixture as lustrous green leaflets meltin at C. It sensitized a gelatinosilver chlorobromide emulsion with maxima at 7 5.80 and 640 mu.

13 Example 28.{4 (1 ethylquinoline)}{2 [4- (2-[ 3ethylbenzoxazolinylidene]ethylidene)- 3 ethyl 5thiazolidone]}methinecyanine iodide 0.488 g. of the quaternary saltobtained in Example 3 above, 0.299 g. of lepldine ethiodide, 0.2 cc. oftriethylamine, and cc. of ethanol were refluxed for 30 minutes, and thesolution then chilled. The precipitate (0.4 g.) was collected on afilter and recrystallized from a methanol-diethyl ether mixture asglittering blue-black crystals melting at 272 C. It sensitized agelatino silver chloride emulsion with a maximum at 6'70 m Example29.-{2 (3 ethylbeneothiazole)}{2- [4 (2 [3ethylbenzomazolinylidenelethylz'dene) 3 methyl 5thz'aeoli-done]}methine-cyamne iodide.

1.6 g. of the quaternary salt obtained in EX- ample 2 above, 0.9 g. of2-methylbenzothiazole ethiodide, 0.5 cc. of triethylamine, and 10 cc. ofethanol were refluxed for 30 minutes and then chilled. The precipitate(0.9 g.) was collected on a filter and recrystallized from pyridine asfine green needles melting at 292 C. It sensitized a gelatino silverchloride emulsion with a maximum at 600 m and a gel-atino silverbromiodide emulsion with a maximum at 630 m Example 30.{2 (3ethylbenzomazole)}{4- [2 (3 ethyl 4 oro 2 thio 5 thiazolidinylz'clene) 3methyl 5 thiazolidonel} dimethine-merocyanine,

1.03 g. of the quaternary salt obtained in Example 2 above, 0.3 g. of3-ethylrhodanine, 0.3 cc. of triethylamine and 10 cc. of ethanol wererefluxed for 10 minutes, and then cooled. The precipitate was collectedon a filter and recrystallized from pyridine as fine mauve needlesmelting above 310 C. It sensitized a gelatino silver chloride emulsionwith a maximum at 600 m and a gelatino silver bromiodide emulsion with amaximum at 630 m Example 31.-{2 (3 ethylbenzothiazole) }{4- [2 (3 ethyl4 omo 2 thio 5 thiaeolidinylidene) 3 ethyl 5 thiazolidonel}dimethine-merocyanine.

1.74 g. of [Z-(B-ethylbenzothiazole)l[4-(2- ethy1thio-5 -thiazol0ne)dimethinemerocya- Example 32.--{2 (3 ethylbeneomazole)}{4- [2-(3-ethyl-4-oro-2-thio-5 thiazolz'dinylidene) 3 ethyl 5 thiaeolidonel}dimethinemero-cyam'nc 1.0 g. of [2-(3-ethylbenzoxazole)l[4-(2-ethylthio5(4) thiazolone)] dimethinemerocyanine and 0.5 g. of ethyl sulfate werefused at C. for 4 hours, and 0.45 g. of 3-ethylrhodanine, 0.5 cc. oftriethylamine and 10 cc. of ethanol were added. The solution wasrefluxed for 10 minutes, and then chilled. The precipitate was collectedon a filter and recrystallized from benzene as steel-blue needlesmelting at 278 C. It sensitized a gelatino silver chloride emulsion witha maximum at 600 m and a gelatino silver bromiodide emulsion with amaximum at 625 m Example 33.-{2 (3 ethylbeneomazole) }{*2- [4 (2 [3ethylbenzothtazoltnylidenelethyltdene) 3 methyl 5 thiazoliclonal}methznecyamne iodide 1.2 g. of the quaternary salt obtained in Example11 above, 0.7 g. of Z-methylbenzoxazole ethiodide, 0.5 cc. oftriethylamine, and 10 cc. of ethanol were refluxed for 10 minutes, andthen chilled. The precipitate was collected on a filter and onrecrystallization was obtained as goldengreen needles melting at 280 C.It sensitized a gelatino silver chloride emulsion with a maximum at 610m and a gelatino silver bromiodide emulsion with a maximum at 635 mExample 34.-{4-(i-ethylquinoline)} {2-[4-2-[3-ethylbenzothiazolinyltdene] ethylidene)-3 methyl- 5-thiazolidonel}methinecyanine io- 1.2 g. of the quaternary salt obtained in Example 11above, 0.8 g. of lepidine ethiodide, 0.5 cc. of triethylamine, and 10cc. of ethanol were refluxed for 10 minutes and then cooled. Theprecipitate was collectedon a filter and washed with ethanol until thewashings were blue. The precipitate was then boiled out several timeswith i5 fresh portions or :methanol. needles melting at 292 C.

It formed ereen 1.2 g. of the quaternary salt obtained in EX- ample 11above, 0.8 g. of 2-.methylbenzothiazole ethiodide, 0.5 cc. oftriethy-lamine, and .1 cc. of ethanol were refluxed for .10 minutes andthen cooled. The precipitate was collected on a filter, and washed withethanol until the washings were blue. It was then boiled out severaltimes with fresh portions of methanol. It formed green needles meltingat 278 C. It sensitized a gelatino silver bromiodide emulsion with amaximum at 650 my" Example 36.-{2-(3-ethylbenzothiaeole)} 4-[2-(Z-n-heptylthz'o 5-oxo-4-thiazolinylidene)-3- methyl .5thz'aaolidonc]}dimethinemerocyanine 0.7 g. of N-(dithiocarbo-n-heptoxy)glycine and 7 cc. of acetic anhydride were heated for minutes on a steambath, and the unreacted acetic anhydride and acetic acid formed duringthe reaction removed under a vacuum. To the residue consisting of2-n-heptylthio-5 (4) -thiazo.lone were added 1.2 g. of the quaternarysalt obtained in Example 11 above, 0.5 cc. of triethylamine, and 10 cc.of ethanol, and the solution was refluxed for 5 minutes and chilled. Theprecipitate was collected on a filter and recrystallized from benzone asfine green needles melting at 200 C. It sensitized a gelatino silverbromide emulsion with a maximum at 645 C.

The N-(dithiocarbo-n-octoxy)glycine used in Example 23 above wasprepared as follows:

Example 37.--N-(.dithiocarbo-n-octowy)glycine 22.4 g. of potassiumhydroxide were dissolved in cc. of water and the solution chilled. Therewere then added 15.0 g. of glycine and 15.2 g. of carbondisulfide, andthe whole shaken mechanically until a clear orange solution resulted. Asolution of 38.6 g. of n-octylamine in 50 cc. of ethanol was added, andthe mixture heated for 30 minutes on a steam bath. To the resultingone-phase solution there were added 100 cc. of water, and the cloudinessresulting removed by extraction with diethyl ether. The aqueous layerwas warmed gently under reduced pressure to expel any dissolved ether,the solution chilled, and acidified with concentrated hydrochloric acid.The precipitate was collected on a filter. washed with water, air-dried,and. recrystallized from petroleum ether (13. P. -80" C.) asglistennsp'lates melting at 100 o.

By replacing the .n-octylamine in Example .3?

.16 by :a moleoularly equivalent amount or .n-heptylamine, Ntdithiocarboen-heptoxy) glycine was obtained as glistening, waxy platesmelting at 99 C. on recrystallization from petroleum ether.

The ,N-Lthiocarbo-n-octoxy) glycine used in Example 27 above wasprepared as follows:

Example 38r-N-tbiocarb0en-octoxy) glycine '1 41101. of n-octylalcoholwas dissolved in.2.5.0 cc. of .carbondisulfide and 1 g. mol. ofpowdered potassium hydroxide was added. The whole was shakenmechanically until it had set to a solid, After chilling overnight, thesalt was collected. washed with diethyl ether, .and airdried.

1 ;g. mol. of the potassium n-octoxydithio- Iormate (potassiumn-octylzanthate) was added to 250 cc. of methanol, and 1 g. mol. ofethylbromide added. The mixture was warmed for several minutes, andwater added. The oil which separated was taken up in diethyl ether,dried over sodium sulfate, and the ether removed by warming under avacuum.

1 g. mol. of the ethyl n-octoxydithioformate (ethyl n-octylzanthate)thus obtained, 1 g. mol. of glycine, 1 g. mol. of potassium hydroxidewere added to 200 cc. of a 50 per cent aqueous ethanol solution, and thewhole refluxed on a steam bath for 18 hours. The solution was thenconcentrated to 00., 100 cc. of water was added, and the solution madeacid with hydrochloric acid. The precipitate of the desired2n-octoxy-5'(4)-thiazo'lone was recrystallized from petroleum other asfine'needles melting at 72 (3.

Operating in a similar manner to that illustrated in the above examples,other trinuelear dyes can be prepared according to our invention. Forexample, by replacing the quaternary salt used in Example 15 by amolecularly equivalent amount of [2-(B-methylbenzothiazole)] [4-(2-methylthio 5(4) thiazolone)l merocyanine metho-p-toluenesulfonate, [2 3methylbenzothiazole)l [4 (5 oxo 2 phenyl 4 oxazolinylidene) -3-methyl-5(4) -thiazolidone) merocyanine represented by the following formula:

din

can be obtained.

In like manner, by replacing the quaternary salt used in Example 18above, by a molecularly equivalent amount of l2-(3-ethy1benzoxazole)l [4.(2 .methylthio 5(4) thiazoloneH tetramethinemerocyaninemetho-p-toluenesulfonate, {.2 (B-methvthiazoline{2-[4-(2-[3-ethy1benzoxazolylidene} 1,3-butadienylidene)-3-methylare)-thiazolonel} methinecyanine iodide represented bythe following formula;

can be obtained.

As shown above we have found thatour new consisting of those representedby the following dyes spectrally sensitive photographic silver generalfgrmulas; halide emulsions when incorporated therein. z Q The dyes areespecially useful for extending the M J: spectral sensitivity of thecustomarily employed B N("CH=CH)-1 73(=L L)d-l= gelatinosilver-chloride, gelatino-silver-chlorobromide, gelatino-silver-bromideand gelatinosilver bromiodide developing-out emulsions. To d o=c-sprepare emulsions sensitized with one or more of wherein R, R1, and R2each represents an alkyl our new dyes, it is only necessary to dispersethe group of the formula C1nH2m+1 wherein m repredye or dyes in theemulsions. The methods of sents a positive integer of from 1 to 8, Lrepreincorporating dyes in emulsions are simple and sents a methinegroup, e and n each represents are known to those skilled in the art. Inpraca positive integer from 1 to 2, d represents a positice, it isconvenient to add the dyes to the emultive integer from 1 to 3, Xrepresents an anion, sions in the form of a solution in an appropriate Qrepresents the non-metallic atoms necessary solvent. Methanol or acetonehas proved satisto complete a heterocyclic nucleus containing 5 factoryas a solvent for most of our new dyes. atoms in the heterocyclic ring, 3of said atoms.

Where the dyes are quite insoluble in methyl being carbon atoms, 1 ofsaid atoms being a alcohol, a mixture of acetone and pyridine isnitrogen atom, and the other of said atoms being advantageously employedas a solvent. The dyes selected from the group consisting of an oxygenare advantageously incorporated in the finished, atom, a sulfur atom,and a nitrogen atom, and Zv washed emulsionsand should be uniformlydisand Z1 each represents the non-metallic atoms tributed throughout theemulsions. The parnecessary to complete a heterocyclic nucleus seticularsolvent used Will, of course, depend on the lected from the groupconsisting of those of the solubility properties of the'particular dye.thiazole series, those of the benzothiazole series,

The concentration of the dyes in the emulsions those of thenaphthothiazole series, those of the can vary widely, e. g. from 5 to100 mg. per liter oxazole series, those of the benzoxazole series, offlowable emulsion. The concentration of the those of the napththoxazoleseries, those of the dyes will vary according to the type of emulsionselenazole series, those of the benzoselenazole' and according to theeffect desired. The suitseries, those of the naphthoselenazole series,able and most economical concentration for any those of the thiazolineseries, those of the 2- given emulsion will be apparent to those skilledin quinoline series, those of the 4-quinoline series,

the art, upon making the ordinary tests and ob- 40 those of thel-isoquinoline series, those of the'3- servations customarily used inthe art of emul isoquinoline series, those of the pyridine series, sionmaking. To prepare a gelatino-silverand those of the3,3-dimethylindolenine series. halide emulsion sensitized with one ormore of 2. The trinuclear dye represented by the folour new dyes, thefollowing procedure is satislowing f rm 1a; factory:

A quantity of dye is dissolved in methyl alco- V hol or acetone (or amixture of acetone and Q Q can pyridine) and a volume of this solution,-which morn =on n= may be diluted with water, containing from 5 to 100mg. of dye, is slowly added to about 1000 cc. 6 I ofgelatino-silver-halide emulsion, with stirring. Hi Stirring is continueduntil the dye is thoroughly The trinuclear dye represented by the m1-dispersed in the emulsion. lowmg formula! With most of our dyes, from 10to 20 mg. of Q S\ dye per liter of gelatino-silver-bromide or 55 (5bromiodide emulsion (containing about 40 g. of silver halide) sufiicesto produce the maximum \N N sensitizing effect. With the finer grainemul- H sions, somewhat larger concentration of dye may I 01H; be neededto produce the maximum sensitizing 6o 4. The trinuclear dye representedby the folefiect. lowing formula:

The above statements are only illustrative, as it will be apparent thatthe dyes can be incorporated in photographic emulsions by any of theC=OHOH=( J t=cnc other methods customarily employed in the art, N

e. g. by bathing a plate or film upon which an 5 emulsion is coated in asolution of the dye in an 1H appropirate solvent. However, bathingmethods 5. The trinuclear dye represented by the folare ordinarily notto be preferred. Emulsions lowing formula: sensitized with the dyes canbe coated on suitable supports, such as glass, cellulose derivativefilm, resin film or paper in the usual manner. CY=CH CH=A 0: =8

What we claim as our invention and desire secured by Letters Patent ofthe United States is: N N s 1. A trinuclear dye selected from the group6, 4111;

esteem 1Q me.- tainuoleazr dye: bx: the; fab lowing formula:

infant-)1.

wherein R-, R1, and E3 eachrepresents arr alkyl group ofthe formula;,QmHzmerr wherein m-representsa positive-integer from 1 to 8; X1represents" agranion; n represents a; positive integer-from If to 2;11:- represents a positive integer-"from 1* to 3'; and" Z; representsthe non-metallicatoms necessary to complete a heterocyolie nucleusselected from thegroup consisting of-those of the thiazole series,thoseof the benzothiazole series; those of the naphthothiazole series,those of theoxazoleseries; thoseof the 'benzoxazole series, those of'the naphthoxazoleseries,- those of? theselenazole series, those; ofthebenzoselenazole series, those of, the, naphthoselenazqle series thoseof the thiazoline series, those of the 2- quinoline series, those ofthe: Q-qpinoline series; those of: the l-isoquinoline series-,- those"of-the- 3- isoquinoline series, those of the pyridine series; and'thoseof" the 3;3"-dimethylindolenine series; with acompoundrelected from thegroup, w n

sisting of a ketomethylene compound selected;

from those, represented by the following, neralj formula:

m6 b= wherein- Q- represents the non-metallic atoms necessary tocompletea heterocyoliolnucleus containing -atoms in the heterocyclicring; 3of said atome-bein icarhoniatoms, 1* f; said; etomebein atnitrogeni atom. and the; otherofi said: atoms e ng; sel atedfrom; thegroup consistin of; an: oxy e atom a sulfun atom: andsanitmgsm atom; andcyolammoniumaquaternary salt; seleotedsimm, thoise: represented by. the;followinggeneral; 103- mu a;

wherein R2 represent an alkyl group of the formula CmHZuH-l wherein mrepresents a positive integer from 1 to 8, X represents an anion, erepresents, a; positi-te integerfrom; 1 to 21 and Z1, represents the:non-metallic, atoms necessary to, complete.- a heterocyolic nueleusselected from the. groupconsisting: of, those; of the thiazole; series,thoseeof the benzot-hiazole series, thoseoh the-naphthothiazole: series,thoseoi the oxazole:

series those of the: henzoxazole; series, thOSB -.-QL. the-naphthoxazo1eseries, those-0 theiselenazolei series, those of theabenzoselenazoleseizies those; of, thefnaphthoselenazole-series, thoseQfithethirazoline; series those: of. the 2-quinoline series, those of;the 4V-quin0line series those,-of the 1,- isoquinoline: series those--.of; thens isoguinoline. series, thosezof the pyridinerseries. andthosemt. the: 3,3-dimethylindoleninee series.

8,; A process, according to, olaimfl; whereimthe;condensationiisperformed in thenresenceottrie eths lamine.-.

BER RQY A.. JWEKSJ,

References Cited in the file of this patent, UNITED Sc'IIA'lIES PATENTS-Number; Name;- Date:

2;l70;80.4; Breaker-"many" Augzlfi; 19397' 223881962 Et'y n Noyes l3,19.455

OTHER REFERENCES 00.9 J, Chem.. Soc,-, (1943), p.11. 1056:4057. Cools,L. Chem, Soc, (1943), li43'5$143?.-,, 2?$2e234fia

1. A TRINUCLEAR DYE SELECTED FROM THE GROUP CONSISTING OF THOSEREPRESENTED BY THE FOLLOWING GENERAL FORMULAS: